WO2018175533A1 - Catalyseurs d'oxydes mélangés pour couplage oxydatif du méthane - Google Patents

Catalyseurs d'oxydes mélangés pour couplage oxydatif du méthane Download PDF

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Publication number
WO2018175533A1
WO2018175533A1 PCT/US2018/023488 US2018023488W WO2018175533A1 WO 2018175533 A1 WO2018175533 A1 WO 2018175533A1 US 2018023488 W US2018023488 W US 2018023488W WO 2018175533 A1 WO2018175533 A1 WO 2018175533A1
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rare earth
earth element
ocm catalyst
ocm
catalyst composition
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PCT/US2018/023488
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English (en)
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Wugeng Liang
David West
Luanyi LI
Vidya Sagar Reddy SARSANI
Hector PEREZ
James W. Kauffman
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Sabic Global Technologies, B.V.
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Priority to US16/495,554 priority Critical patent/US11458458B2/en
Publication of WO2018175533A1 publication Critical patent/WO2018175533A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/04—Ethylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
    • C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons
    • C07C9/02—Aliphatic saturated hydrocarbons with one to four carbon atoms
    • C07C9/04—Methane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present disclosure relates to catalyst compositions for oxidative coupling of methane (OCM), more specifically catalyst compositions based on oxides of alkaline earth metals, La, and optionally redox agents and/or rare earth elements for OCM, and methods of making and using same.
  • OCM oxidative coupling of methane
  • Hydrocarbons and specifically olefins such as ethylene, are typically building blocks used to produce a wide range of products, for example, break-resistant containers and packaging materials.
  • ethylene is produced by heating natural gas condensates and petroleum distillates, which include ethane and higher hydrocarbons, and the produced ethylene is separated from a product mixture by using gas separation processes.
  • Oxidative coupling of the methane (OCM) has been the target of intense scientific and commercial interest for more than thirty years due to the tremendous potential of such technology to reduce costs, energy, and environmental emissions in the production of ethylene (C 2 H 4 ).
  • OCM methane
  • oxygen (0 2 ) react exothermically over a catalyst to form C 2 H 4 , water (H 2 0) and heat.
  • Ethylene can be produced by OCM as represented by Equations (I) and (II):
  • CH 4 is first oxidatively converted into ethane (C 2 H 6 ), and then into C 2 H .
  • CH 4 is activated heterogeneously on a catalyst surface, forming methyl free radicals (e.g., CH 3 *), which then couple in a gas phase to form C 2 H 6 .
  • C 2 H 6 subsequently undergoes dehydrogenation to form C 2 H 4 .
  • An overall yield of desired C 2 hydrocarbons is reduced by non-selective reactions of methyl radicals with oxygen on the catalyst surface and/or in the gas phase, which produce (undesirable) carbon monoxide and carbon dioxide.
  • an oxidative coupling of methane (OCM) catalyst composition characterized by the general formula A a La b E c D d O x ; wherein A is an alkaline earth metal; wherein E is a first rare earth element; wherein D is a redox agent or a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein c is from about 0 to about 10.0; wherein d is from about 0 to about 10.0; and wherein x balances the oxidation states.
  • OCM methane
  • a method of making an oxidative coupling of methane (OCM) catalyst composition comprising (a) forming an OCM catalyst precursor mixture; wherein the OCM catalyst precursor mixture comprises one or more compounds comprising an alkaline earth metal cation, one or more compounds comprising a La cation, one or more compounds comprising a first rare earth element cation, and one or more compounds comprising a redox agent cation or a second rare earth element cation; wherein the first rare earth element cation and the second rare earth element cation are different; wherein the OCM catalyst precursor mixture is characterized by a molar ratio of La to alkaline earth metal of b: l, wherein b is from about 0.01 to about 10.0; wherein the OCM catalyst precursor mixture is characterized by a molar ratio of first rare earth element to alkaline earth metal of c: l, wherein c is from about 0 to about 10.0; and wherein the OCM catalyst precursor mixture is
  • a method of making an oxidative coupling of methane (OCM) catalyst composition comprising (a) forming an OCM catalyst precursor aqueous solution comprising an alkaline earth metal nitrate, a La nitrate, a first rare earth element nitrate, and a redox agent nitrate or a second rare earth element nitrate; wherein the first rare earth element nitrate and the second rare earth element nitrate are different; wherein the OCM catalyst precursor aqueous solution is characterized by a molar ratio of La to alkaline earth metal of b: l, wherein b is from about 0.01 to about 10.0; wherein the OCM catalyst precursor aqueous solution is characterized by a molar ratio of first rare earth element to alkaline earth metal of c: l, wherein c is from about 0 to about 10.0; and wherein the OCM catalyst precursor aqueous solution is characterized by a molar ratio of
  • an oxidative coupling of methane (OCM) catalyst composition produced by (a) solubilizing one or more compounds comprising an alkaline earth metal cation, one or more compounds comprising a La cation, one or more compounds comprising a first rare earth element cation, and one or more compounds comprising a redox agent cation or second rare earth element cation in an aqueous medium to form an OCM catalyst precursor aqueous solution; wherein the first rare earth element cation and the second rare earth element cation are different; wherein the OCM catalyst precursor aqueous solution is characterized by a molar ratio of La to alkaline earth metal of b: l, wherein b is from about 0.01 to about 10.0; wherein the OCM catalyst precursor aqueous solution is characterized by a molar ratio of first rare earth element to alkaline earth metal of c: l, wherein c is from about 0 to about 10.0; and wherein the OCM catalyst precursor aqueous solution
  • a method for producing olefins comprising (a) introducing a reactant mixture to a reactor comprising an oxidative coupling of methane (OCM) catalyst composition; wherein the reactant mixture comprises methane (CH 4 ) and oxygen (0 2 ); wherein the OCM catalyst composition is characterized by the general formula A a La b E c D d O x ; wherein A is an alkaline earth metal; wherein E is a first rare earth element; wherein D is a redox agent or a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein c is from about 0 to about 10.0; wherein d is from about 0 to about 10.0; and wherein x balances the oxidation states; (b) allowing at least a portion of the reactant mixture to contact at least a portion of the OCM catalyst composition and
  • Figure 1 displays a graph of 0 2 conversion in an OCM reaction over time for different catalysts
  • Figure 2 displays a graph of CH 4 conversion, and C 2+ selectivity in an OCM reaction over time.
  • an OCM catalyst composition can be characterized by the general formula A a La b E c D d O x ; wherein A is an alkaline earth metal; wherein E is a first rare earth element; wherein D is a redox agent or a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein c is from about 0 to about 10.0; wherein d is from about 0 to about 10.0; and wherein x balances the oxidation states.
  • a method of making an OCM catalyst composition can generally comprise the steps of (a) forming an OCM catalyst precursor mixture; wherein the OCM catalyst precursor mixture comprises one or more compounds comprising an alkaline earth metal cation, one or more compounds comprising a La cation, one or more compounds comprising a first rare earth element cation, and one or more compounds comprising a redox agent cation or a second rare earth element cation; wherein the first rare earth element cation and the second rare earth element cation are different; wherein the OCM catalyst precursor mixture is characterized by a molar ratio of La to alkaline earth metal of b: l, wherein b is from about 0.01 to about 10.0; wherein the OCM catalyst precursor mixture is characterized by a molar ratio of first rare earth element to alkaline earth metal of c: l, wherein c is from about 0 to about 10.0; and wherein the OCM catalyst precursor mixture is characterized by a molar ratio of redox agent
  • the one or more compounds comprising an alkaline earth metal cation can comprise an alkaline earth metal nitrate, an alkaline earth metal oxide, an alkaline earth metal hydroxide, an alkaline earth metal chloride, an alkaline earth metal acetate, an alkaline earth metal carbonate, and the like, or combinations thereof;
  • the one or more compounds comprising a La cation can comprise a La nitrate, a La oxide, a La hydroxide, a La chloride, a La acetate, a La carbonate, and the like, or combinations thereof;
  • the one or more compounds comprising a first rare earth element cation can comprise a first rare earth element nitrate, a first rare earth element oxide, a first rare earth element hydroxide, a first rare earth element chloride, a first rare earth element acetate, a first rare earth element carbonate, and the like, or combinations thereof;
  • the one or more compounds comprising a redox agent cation can comprise a
  • the terms “inhibiting” or “reducing” or “preventing” or “avoiding” or any variation of these terms include any measurable decrease or complete inhibition to achieve a desired result.
  • the term "effective,” means adequate to accomplish a desired, expected, or intended result.
  • the terms “comprising” (and any form of comprising, such as “comprise” and “comprises"), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “include” and “includes”) or “containing” (and any form of containing, such as “contain” and “contains”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
  • a method for producing olefins as disclosed herein can comprise introducing a reactant mixture to a reactor comprising an oxidative coupling of methane (OCM) catalyst composition to form a product mixture comprising olefins, wherein the reactant mixture comprises methane (CH 4 ) and oxygen (0 2 ), and wherein the OCM catalyst composition can be characterized by the general formula A a La b E c D d O x ; wherein A is an alkaline earth metal; wherein E is a first rare earth element; wherein D is a redox agent or a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein c is from about 0 to about 10.0; wherein d is from about 0 to about 10.0; and wherein x balances the oxidation states.
  • OCM methane
  • the reactant mixture can be a gaseous mixture.
  • the reactant mixture can comprise a hydrocarbon or mixtures of hydrocarbons, and oxygen.
  • the hydrocarbon or mixtures of hydrocarbons can comprise natural gas (e.g., CH 4 ), liquefied petroleum gas comprising C 2 -C 5 hydrocarbons, C 6 + heavy hydrocarbons (e.g., C 6 to C 24 hydrocarbons such as diesel fuel, jet fuel, gasoline, tars, kerosene, etc.), oxygenated hydrocarbons, biodiesel, alcohols, dimethyl ether, and the like, or combinations thereof.
  • the reactant mixture can comprise CH 4 and 0 2 .
  • the 0 2 used in the reactant mixture can be oxygen gas (which may be obtained via a membrane separation process), technical oxygen (which may contain some air), air, oxygen enriched air, and the like, or combinations thereof.
  • the reactant mixture can further comprise a diluent.
  • the diluent is inert with respect to the OCM reaction, e.g., the diluent does not participate in the OCM reaction.
  • the diluent can comprise water, nitrogen, inert gases, and the like, or combinations thereof.
  • the diluent can provide for heat control of the OCM reaction, e.g., the diluent can act as a heat sink.
  • an inert compound e.g., a diluent
  • the diluent can be present in the reactant mixture in an amount of from about 0.5% to about 80%, alternatively from about 5% to about 50%, or alternatively from about 10% to about 30%, based on the total volume of the reactant mixture.
  • a method for producing olefins can comprise introducing the reactant mixture to a reactor, wherein the reactor comprises the OCM catalyst composition disclosed herein.
  • the reactor can comprise an adiabatic reactor, an autothermal reactor, an isothermal reactor, a tubular reactor, a cooled tubular reactor, a continuous flow reactor, a fixed bed reactor, a fluidized bed reactor, a moving bed reactor, and the like, or combinations thereof.
  • the reactor can comprise an adiabatic reactor.
  • the reactor can comprise a catalyst bed comprising the OCM catalyst composition disclosed herein.
  • the reactant mixture can be introduced to the reactor at a temperature of from about 150°C to about 1,000°C, alternatively from about 225°C to about 900°C, or alternatively from about 250°C to about 800°C.
  • a temperature of from about 150°C to about 1,000°C, alternatively from about 225°C to about 900°C, or alternatively from about 250°C to about 800°C.
  • the reactant mixture can be introduced to the reactor at a temperature effective to promote an OCM reaction.
  • the reactor can be characterized by a temperature of from about 400°C to about 1,200°C, alternatively from about 500°C to about 1,100°C, or alternatively from about 600°C to about 1,000°C.
  • the reactor can be characterized by a pressure of from about ambient pressure (e.g., atmospheric pressure) to about 500 psig, alternatively from about ambient pressure to about 200 psig, or alternatively from about ambient pressure to about 150 psig.
  • the method for producing olefins as disclosed herein can be carried out at ambient pressure.
  • the reactor can be characterized by a gas hourly space velocity (GHSV) of from about 500 h “1 to about 10,000,000 h “1 , alternatively from about 500 h “1 to about 1,000,000 h “1 , alternatively from about 500 h “1 to about 500,000 h “1 , alternatively from about 1,000 h “1 to about 500,000 h “1 , alternatively from about 1,500 h “1 to about 500,000 h “1 , alternatively from about 2,000 h “1 to about 500,000 h “1 , alternatively from about 5,000 h “1 to about 500,000 h “1 , alternatively from about 10,000 h "1 to about 500,000 h “1 , or alternatively from about 50,000 h “1 to about 500,000 h “1 .
  • GHSV gas hourly space velocity
  • the GHSV relates a reactant (e.g., reactant mixture) gas flow rate to a reactor volume.
  • GHSV is usually measured at standard temperature and pressure.
  • the reactor can comprise an OCM catalyst composition as disclosed herein characterized by the general formula A a La b E c D d O x ; wherein A is an alkaline earth metal; wherein E is a first rare earth element; wherein D is a redox agent or a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0.01 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5; wherein c is from about 0 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5; wherein d is from about 0 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5; and wherein x balances the oxidation states.
  • each of the A, La, E and D can have multiple oxidation states within the OCM catalyst composition, and as such x can have any suitable value that allows for the oxygen anions to balance all the cations.
  • the different metals (A, La, E, and D) present in the OCM catalyst compositions as disclosed herein display synergetic effects in terms of conversion and selectivity.
  • the OCM catalyst composition as disclosed herein can comprise an alkaline earth metal (A).
  • the alkaline earth metal (A) can be selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and combinations thereof.
  • the alkaline earth metal (A) is strontium (Sr).
  • the OCM catalyst composition as disclosed herein can comprise a first rare earth element (E) and/or a second rare earth element (D), wherein E and D are different.
  • the first rare earth element (E) and the second rare earth element (D) can each independently be selected from the group consisting of scandium (Sc), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), yttrium (Y), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), and combinations thereof.
  • the OCM catalyst composition as disclosed herein can comprise a redox agent (D).
  • D can be either a redox agent or a second rare earth element.
  • the redox agent (D) can be selected from the group consisting of manganese (Mn), tungsten (W), bismuth (Bi), antimony (Sb), tin (Sn), cerium (Ce), praseodymium (Pr), and combinations thereof.
  • a redox agent generally refers to a chemical species that possesses the ability to undergo both an oxidation reaction and a reduction reaction, and such ability usually resides in the chemical species having more than one stable oxidation state other than the oxidation state of zero (0).
  • some rare earth elements such as Ce and Pr, can also be considered redox agents.
  • D when D is Ce and/or Pr, D can be considered either a redox agent or a second rare earth element.
  • the redox agent (D) is manganese (Mn). In other aspects, the redox agent (D) is tungsten (W).
  • the first rare earth element (E) and/or the second rare earth element (D) can be basic (e.g., can exhibit some degree of basicity; can have affinity for hydrogen; can exhibit some degree of affinity for hydrogen).
  • rare earth elements that can be considered basic for purposes of the disclosure herein include scandium (Sc), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), yttrium (Y), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), and combinations thereof.
  • the OCM reaction is a multi-step reaction, wherein each step of the OCM reaction could benefit from specific OCM catalytic properties.
  • an OCM catalyst should exhibit some degree of basicity to abstract a hydrogen from CH 4 to form hydroxyl groups [OH] on the OCM catalyst surface, as well as methyl radicals (CH 3 *).
  • an OCM catalyst should exhibit oxidative properties for the OCM catalyst to convert the hydroxyl groups [OH] from the catalyst surface to water, which can allow for the OCM reaction to continue (e.g., propagate).
  • an OCM catalyst could also benefit from properties like oxygen ion conductivity and proton conductivity, which properties can be critical for the OCM reaction to proceed at a very high rate (e.g., its highest possible rate).
  • an OCM catalyst comprising a single metal might not provide all the necessary properties for an optimum OCM reaction (e.g., best OCM reaction outcome) at the best level, and as such conducting an optimum OCM reaction may require an OCM catalyst with tailored composition in terms of metals present, wherein the different metals can have optimum properties for various OCM reaction steps, and wherein the different metals can provide synergistically for achieving the best performance for the OCM catalyst in an OCM reaction.
  • the OCM catalyst composition as disclosed herein can comprise one or more oxides of A; one or more oxides of La; one or more oxides of E; one or more oxides of D; or combinations thereof.
  • the OCM catalyst composition can comprise one or more oxides of a metal, wherein the metal comprises A, La, and optionally E and/or D.
  • the OCM catalyst composition can comprise, consist of, or consist essentially of the one or more oxides.
  • the one or more oxides can be present in the OCM catalyst composition in an amount of from about 0.01 wt.% to about 100.0 wt.%, alternatively from about 10.0 wt.% to about 90.0 wt.%, or alternatively from about 30.0 wt.% to about 70.0 wt.%, based on the total weight of the OCM catalyst composition.
  • a portion of the one or more oxides, in the presence of water, such as atmospheric moisture can convert to hydroxides, and it is possible that the OCM catalyst composition will comprise some hydroxides, due to exposing the OCM catalyst composition comprising the one or more oxides to water (e.g., atmospheric moisture).
  • a portion of the one or more oxides, in the presence of carbon dioxide, such as atmospheric carbon dioxide can convert to carbonates, and it is possible that the OCM catalyst composition will comprise some carbonates, due to exposing the OCM catalyst composition comprising the one or more oxides to carbon dioxide (e.g., atmospheric carbon dioxide).
  • the one or more oxides can comprise a single metal oxide, mixtures of single metal oxides, a mixed metal oxide, mixtures of mixed metal oxides, mixtures of single metal oxides and mixed metal oxides, or combinations thereof.
  • the single metal oxide comprises one metal selected from the group consisting of A, La, E, and D.
  • a single metal oxide can be characterized by the general formula M m O y ; wherein M is the metal selected from the group consisting of A, La, E, and D; and wherein m and y are integers from 1 to 7, alternatively from 1 to 5, or alternatively from 1 to 3.
  • a single metal oxide contains one and only one metal cation.
  • Nonlimiting examples of single metal oxides suitable for use in the OCM catalyst compositions of the present disclosure include CaO, MgO, SrO, BaO, La 2 0 3 , Sc 2 0 3 , Y 2 0 3 , Ce0 2 , Ce 2 0 3 , Pr 2 0 3 , Pr0 2 , Nd 2 0 3 , Pm 2 0 3 , Sm 2 0 3 , Eu 2 0 3 , Gd 2 0 3 , Tb 2 0 3 , Dy 2 0 3 , Ho 2 0 3 , Er 2 0 3 , Lu 2 0 3 , Yb 2 0 3 , Tm 2 0 3 , W0 3 , Mn0 2 , W 2 0 3 , Sn0 2 , and the like, or combinations thereof.
  • mixtures of single metal oxides can comprise two or more different single metal oxides, wherein the two or more different single metal oxides have been mixed together to form the mixture of single metal oxides.
  • Mixtures of single metal oxides can comprise two or more different single metal oxides, wherein each single metal oxide can be selected from the group consisting of CaO, MgO, SrO, BaO, La 2 0 3 , Sc 2 0 3 , Y 2 0 3 , Ce0 2 , Ce 2 0 3 , Pr 2 0 3 , Pr0 2 , Nd 2 0 3 , Pm 2 0 3 , Sm 2 0 3 , Eu 2 0 3 , Gd 2 0 3 , Tb 2 0 3 , Dy 2 0 3 , Ho 2 0 , Er 2 0 , Lu 2 0 , Yb 2 0 , Tm 2 0 , W0 , Mn0 2 , W 2 0 , and Sn0 2 .
  • Nonlimiting examples of mixtures of single metal oxides suitable for use in the OCM catalyst compositions of the present disclosure include SrO- La 2 0 3 , SrO-MgO-La 2 0 3 , SrO-Yb 2 0 3 -La 2 0 3 , SrO-Er 2 0 3 -La 2 0 3> SrO-Ce0 2 -La 2 0 3 , SrO-Mn0 2 -La 2 0 3 , SrO- W0 3 -W 2 0 3 -La 2 0 3 , SrO-W0 3 -Tm 2 0 3 -La 2 0 3 , SrO-W0 3 -Tm 2 0 3 -La 2 0 3 , SrO-BaO-Ce0 2 -Er 2 0 3 -La 2 0 3 , SrO- Ce0 2 -Ce 2 0 3 -Er 2 0 3 -La 2 0 3 , Sr
  • the mixed metal oxide comprises two or more different metals, wherein each metal can be independently selected from the group consisting of A, La, E, and D.
  • a mixed metal oxide can be characterized by the general formula M 1 m iM 2 m2 O y ; wherein M 1 and M 2 are metals; wherein each of the M 1 and M 2 can be independently selected from the group consisting of A, La, E, and D; and wherein ml , m2 and y are integers from 1 to 15, alternatively from 1 to 10, or alternatively from 1 to 7.
  • M 1 and M 2 can be metal cations of different chemical elements, for example M 1 can be a lanthanum cation and M 2 can be a strontium cation.
  • M 1 and M 2 can be different cations of the same chemical element, wherein M 1 and M 2 can have different oxidation states.
  • the mixed metal oxide can comprise Mn 3 0 4 , wherein M 1 can be a Mn (II) cation and M 2 can be a Mn (III) cation.
  • Nonlimiting examples of mixed metal oxides suitable for use in the OCM catalyst compositions of the present disclosure include La/SrO; LaYb0 3 ; SrYb 2 0 4 ; Sr 2 Ce0 4 ; Mn 3 0 4 ; La/MgO; Sm 2 Ce 2 0 7 ; Er 2 Ce 2 0 7 ; CaTm 2 0 4 ; MgYb 2 0 4 ; SrCe (1 . y) Yb y 0 , wherein y can be from about 0.01 to about 0.99; and the like; or combinations thereof.
  • mixtures of mixed metal oxides can comprise two or more different mixed metal oxides, wherein the two or more different mixed metal oxides have been mixed together to form the mixture of mixed metal oxides.
  • Mixtures of mixed metal oxides can comprise two or more different mixed metal oxides, such as La/SrO; LaYb0 3 ; SrYb 2 0 4 ; Sr 2 Ce0 4 ; Mn 3 0 4 ; La/MgO; Sm 2 Ce 2 0 7 ; Er 2 Ce 2 0 7 ; CaTm 2 0 4 ; MgYb 2 0 4 ; SrCe(i.y ) Yb y 0 3 , wherein y can be from about 0.01 to about 0.99; and the like; or combinations thereof.
  • mixtures of single metal oxides and mixed metal oxides can comprise at least one single metal oxide and at least one mixed metal oxide, wherein the at least one single metal oxide and the at least one mixed metal oxide have been mixed together to form the mixture of single metal oxides and mixed metal oxides.
  • the OCM catalyst compositions suitable for use in the present disclosure can be supported OCM catalyst compositions and/or unsupported OCM catalyst compositions.
  • the supported OCM catalyst compositions can comprise a support, wherein the support can be catalytically active (e.g., the support can catalyze an OCM reaction, such as MgO).
  • the supported OCM catalyst compositions can comprise a support, wherein the support can be catalytically inactive (e.g., the support cannot catalyze an OCM reaction, such as Si0 2 ).
  • the supported OCM catalyst compositions can comprise a catalytically active support and a catalytically inactive support.
  • Nonlimiting examples of a support suitable for use in the present disclosure include MgO, A1 2 0 3 , Si0 2 , Zr0 2 , Ti0 2 , and the like, or combinations thereof.
  • the support can be purchased or can be prepared by using any suitable methodology, such as for example precipitation/co-precipitation, sol-gel techniques, templates/surface derivatized metal oxides synthesis, solid-state synthesis of mixed metal oxides, microemulsion techniques, solvothermal techniques, sonochemical techniques, combustion synthesis, etc.
  • the OCM catalyst composition can further comprise a support, wherein at least a portion of the OCM catalyst composition contacts, coats, is embedded in, is supported by, and/or is distributed throughout at least a portion of the support.
  • the support can be in the form of powders, particles, pellets, monoliths, foams, honeycombs, and the like, or combinations thereof.
  • support particle shapes include cylindrical, discoidal, spherical, tabular, ellipsoidal, equant, irregular, cubic, acicular, and the like, or combinations thereof.
  • the OCM catalyst composition can further comprise a porous support.
  • a porous material e.g., support
  • a porous material can provide for an enhanced surface area of contact between the OCM catalyst composition and the reactant mixture, which in turn would result in a higher CH4 conversion to
  • the OCM catalyst composition can be made by using any suitable methodology.
  • a method of making an OCM catalyst composition can comprise a step of forming an OCM catalyst precursor mixture, wherein the OCM catalyst precursor mixture comprises one or more compounds comprising an alkaline earth metal (A) cation, one or more compounds comprising a La cation, one or more compounds comprising a first rare earth element (E) cation, and one or more compounds comprising a redox agent cation or a second rare earth element (D) cation; and wherein the first rare earth element cation and the second rare earth element cation are different.
  • A alkaline earth metal
  • E first rare earth element
  • D second rare earth element
  • the OCM catalyst precursor mixture can be characterized by a molar ratio of La to alkaline earth metal of b: l, wherein b is from about 0.01 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5.
  • the OCM catalyst precursor mixture can be characterized by a molar ratio of first rare earth element to alkaline earth metal of c: l, wherein c is from about 0 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5.
  • the OCM catalyst precursor mixture can be characterized by a molar ratio of redox agent or second rare earth element to alkaline earth metal of d: l, wherein d is from about 0 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5.
  • the one or more compounds comprising an alkaline earth metal cation can comprise an alkaline earth metal nitrate, an alkaline earth metal oxide, an alkaline earth metal hydroxide, an alkaline earth metal chloride, an alkaline earth metal acetate, an alkaline earth metal carbonate, and the like, or combinations thereof.
  • the one or more compounds comprising a La cation can comprise a La nitrate, a La oxide, a La hydroxide, a La chloride, a La acetate, a La carbonate, and the like, or combinations thereof.
  • the one or more compounds comprising a first rare earth element cation can comprise a first rare earth element nitrate, a first rare earth element oxide, a first rare earth element hydroxide, a first rare earth element chloride, a first rare earth element acetate, a first rare earth element carbonate, and the like, or combinations thereof.
  • the one or more compounds comprising a redox agent cation can comprise a redox agent nitrate, a redox agent oxide, a redox agent hydroxide, a redox agent chloride, a redox agent acetate, a redox agent carbonate, and the like, or combinations thereof.
  • the one or more compounds comprising a second rare earth element cation can comprise a second rare earth element nitrate, a second rare earth element oxide, a second rare earth element hydroxide, a second rare earth element chloride, a second rare earth element acetate, a second rare earth element carbonate, and the like, or combinations thereof.
  • the step of forming the OCM catalyst precursor mixture can comprise (i) solubilizing the one or more compounds comprising an alkaline earth metal cation, one or more compounds comprising a La cation, one or more compounds comprising a first rare earth element cation, and one or more compounds comprising a redox agent cation or a second rare earth element cation in an aqueous medium to form an OCM catalyst precursor aqueous solution.
  • the aqueous medium can be water, or an aqueous solution.
  • the OCM catalyst precursor aqueous solution can be formed by dissolving the one or more compounds comprising an alkaline earth metal cation, one or more compounds comprising a La cation, one or more compounds comprising a first rare earth element cation, one or more compounds comprising a redox agent cation or a second rare earth element cation, or combinations thereof, in water or any suitable aqueous medium.
  • the one or more compounds comprising an alkaline earth metal cation, one or more compounds comprising a La cation, one or more compounds comprising a first rare earth element cation, and one or more compounds comprising a redox agent cation or a second rare earth element cation can be dissolved in an aqueous medium in any suitable order.
  • the one or more compounds comprising an alkaline earth metal cation, one or more compounds comprising a La cation, one or more compounds comprising a first rare earth element cation, and one or more compounds comprising a redox agent cation or a second rare earth element cation can be first mixed together and then dissolved in an aqueous medium.
  • the OCM catalyst precursor aqueous solution can be dried to form the OCM catalyst precursor mixture.
  • at least a portion of the OCM catalyst precursor aqueous solution can be dried at a temperature of equal to or greater than about 75°C, alternatively of equal to or greater than about 100°C, or alternatively of equal to or greater than about 125°C, to yield the OCM catalyst precursor mixture.
  • the OCM catalyst precursor aqueous solution can be dried for a time period of equal to or greater than about 4 hours, alternatively equal to or greater than about 8 hours, or alternatively equal to or greater than about 12 hours.
  • a method of making an OCM catalyst composition can comprise a step of calcining at least a portion of the OCM catalyst precursor mixture to form the OCM catalyst composition, wherein the OCM catalyst composition is characterized by the general formula A a La b E c D d O x ; wherein A is an alkaline earth metal; wherein E is a first rare earth element; wherein D is a redox agent or a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein c is from about 0 to about 10.0; wherein d is from about 0 to about 10.0; and wherein x balances the oxidation states.
  • the OCM catalyst precursor mixture can be calcined at a temperature of equal to or greater than about 750°C, alternatively equal to or greater than about 800°C, or alternatively equal to or greater than about 900°C, to yield the OCM catalyst composition.
  • the OCM catalyst precursor mixture can be calcined for a time period of equal to or greater than about 2 hours, alternatively equal to or greater than about 4 hours, or alternatively equal to or greater than about 6 hours.
  • At least a portion of the OCM catalyst precursor mixture can be calcined in an oxidizing atmosphere (e.g., in an atmosphere comprising oxygen, for example in air) to form the OCM catalyst composition.
  • an oxidizing atmosphere e.g., in an atmosphere comprising oxygen, for example in air
  • the oxygen in the OCM catalyst compositions characterized by the general formula A a La b E c D d O x can originate in the oxidizing atmosphere used for calcining the OCM catalyst precursor mixture.
  • the oxygen in the OCM catalyst compositions characterized by the general formula A a La b E c D d O x can originate in the one or more compounds comprising an alkaline earth metal cation, one or more compounds comprising a La cation, one or more compounds comprising a first rare earth element cation, and one or more compounds comprising a redox agent cation or a second rare earth element cation, provided that at least one of these compounds comprises oxygen in its formula, as is the case with nitrates, oxides, hydroxides, acetates, carbonates, etc.
  • the method of making an OCM catalyst composition can further comprise contacting the OCM catalyst composition with a support to yield a supported catalyst (e.g., an OCM supported catalyst, an OCM supported catalyst composition, etc.).
  • a supported catalyst e.g., an OCM supported catalyst, an OCM supported catalyst composition, etc.
  • the method of making an OCM catalyst composition can comprise forming the OCM catalyst composition in the presence of the support, such that the resulting OCM catalyst composition (after the calcining step) comprises the support.
  • the resulting OCM catalyst composition (after the calcining step) comprises the support.
  • at least a portion of the OCM catalyst precursor aqueous solution can be contacted with a support to yield a supported OCM catalyst precursor.
  • at least a portion of the supported OCM catalyst precursor can be further dried (e.g., at a temperature of equal to or greater than about 75°C) and calcined (e.g., at a temperature of equal to or greater than about 750°C) to form the OCM catalyst composition.
  • a method for producing olefins can comprise allowing at least a portion of the reactant mixture to contact at least a portion of the OCM catalyst composition and react via an OCM reaction to form a product mixture comprising olefins.
  • the product mixture comprises coupling products, partial oxidation products (e.g., deep oxidation products, partial conversion products, such as CO, H 2 , C0 2 ), and unreacted methane.
  • the coupling products can comprise olefins (e.g., alkenes, characterized by a general formula C n H 2n ) and paraffins (e.g., alkanes, characterized by a general formula C n H 2n+2 ).
  • the product mixture can comprise C 2+ hydrocarbons, wherein the C 2+ hydrocarbons can comprise C 2 hydrocarbons and C 3 hydrocarbons.
  • the C 2+ hydrocarbons can further comprise C 4 hydrocarbons (C 4 s), such as for example butane, iso-butane, n-butane, butylene, etc.
  • the C 2 hydrocarbons can comprise ethylene (C 2 H 4 ) and ethane (C 2 H 6 ).
  • the C 2 hydrocarbons can further comprise acetylene (C 2 H 2 ).
  • the C 3 hydrocarbons can comprise propylene (C 3 H 6 ) and propane (C 3 H 8 ).
  • the OCM catalyst composition as disclosed herein can be characterized by a CH 4 conversion that is increased by equal to or greater than about 1%, alternatively equal to or greater than about 2%, alternatively equal to or greater than about 5%, or alternatively equal to or greater than about 10%, when compared to a CFL conversion of an otherwise similar OCM catalyst composition (i) without La, or (ii) comprising an alkaline earth metal and La in a La to the alkaline earth metal molar ratio other than from about 0.01 : 1 to about 10.0: 1.
  • a conversion of a reagent or reactant refers to the percentage (usually mol%) of reagent that reacted to both undesired and desired products, based on the total amount (e.g., moles) of reagent present before any reaction took place.
  • the conversion of a reagent is a % conversion based on moles converted.
  • the 0 2 conversion for the OCM as disclosed herein can be equal to or greater than about 90%, alternatively equal to or greater than about 95%, alternatively equal to or greater than about 99%), alternatively equal to or greater than about 99.9%, or alternatively about 100%).
  • the reactant mixture in OCM reactions is generally characterized by a methane to oxygen molar ratio of greater than 1 : 1, and as such the 0 2 conversion is fairly high in OCM processes, most often approaching 90%-100%.
  • oxygen is usually a limiting reagent in OCM processes.
  • the OCM catalyst composition as disclosed herein can be characterized by a reactor temperature effective for achieving an 0 2 conversion of equal to or greater than about 90%> that is decreased by equal to or greater than about 25°C, alternatively by equal to or greater than about 50°C, alternatively by equal to or greater than about 75°C, or alternatively by equal to or greater than about 100°C, when compared to a reactor temperature effective for achieving an 0 2 conversion of equal to or greater than about 90%) of an otherwise similar OCM catalyst composition (i) without La, or (ii) comprising an alkaline earth metal and La in a La to the alkaline earth metal molar ratio other than from about 0.01 : 1 to about 10.0: 1.
  • the OCM catalyst composition as disclosed herein can be characterized by a reactor temperature effective for achieving an 0 2 conversion of equal to or greater than about 90% of less than about 700°C, alternatively less than about 600°C, or alternatively less than about 500°C.
  • the reactor temperature effective for achieving an 0 2 conversion of equal to or greater than about 90% is dependent upon specific reactor conditions, such as for example methane to oxygen molar ratio, type and size of reactor, GHSV, etc.
  • the OCM catalyst composition as disclosed herein can be characterized by a C 2+ selectivity that is increased by equal to or greater than about 2%, alternatively equal to or greater than about 5%, alternatively equal to or greater than about 10%, alternatively equal to or greater than about 15%, or alternatively equal to or greater than about 20%, when compared to a C 2+ selectivity of an otherwise similar OCM catalyst composition (i) without La, or (ii) comprising an alkaline earth metal and La in a La to the alkaline earth metal molar ratio other than from about 0.01 : 1 to about 10.0: 1.
  • a selectivity to a desired product or products refers to how much desired product was formed divided by the total products formed, both desired and undesired.
  • the selectivity to a desired product is a % selectivity based on moles converted into the desired product.
  • a C x selectivity (e.g., C 2 selectivity, C 2+ selectivity, etc.) can be calculated by dividing a number of moles of carbon (C) from CH 4 that were converted into the desired product (e.g., C C2H 4, C C2H 6, etc.) by the total number of moles of C from CH 4 that were converted (e.g., C C2H 4, C C2H 6, C C2H 2, Cc3H6, C C3H 8, C c4s , C C0 2, C c0 , etc.).
  • C C2H 4 number of moles of C from CH 4 that were converted into C 2 H 4 ;
  • C C2H 6 number of moles of C from CH 4 that were converted into C 2 H 6 ;
  • C C2H 2 number of moles of C from CH that were converted into C 2 H 2 ;
  • C C3H6 number of moles of C from CH that were converted into C 3 H 6 ;
  • C C 3 HS number of moles of C from CH that were converted into C 3 H 8 ;
  • C C4s number of moles of C from CH that were converted into C hydrocarbons (C s);
  • C C o2 number of moles of C from CH that were converted into C0 2 ;
  • C C o number of moles of C from CFL that were converted into CO; etc.
  • a C 2+ selectivity refers to how much C 2 H 4 , C 3 H 6 , C 2 H 2 , C 2 H 6 , C 3 H 8 , and C s were formed divided by the total products formed, including C 2 FL t , C 3 H 6 , C 2 H 2 , C 2 H 6 , C 3 H 8 , C s, C0 2 and CO.
  • the C 2+ selectivity can be calculated by using equation (3): selectivity 2 c 2 H 4 + 2 c 2 H 6 + 2 Cc 2 H 2 + 3 c 3 3 ⁇ 4 + 3 c 3 3 ⁇ 4 + Cc 4s x l00%
  • the OCM catalyst composition as disclosed herein can be characterized by a CH 4 conversion that is increased by equal to or greater than about 1 %, alternatively equal to or greater than about 2%, alternatively equal to or greater than about 5%, or alternatively equal to or greater than about 10%; and by a C 2+ selectivity that is increased by equal to or greater than about 2%, alternatively equal to or greater than about 5%, alternatively equal to or greater than about 10%, alternatively equal to or greater than about 15%), or alternatively equal to or greater than about 20%>; when compared to a CH 4 conversion and a C 2+ selectivity, respectively, of an otherwise similar OCM catalyst composition (i) without La, or (ii) comprising an alkaline earth metal and La in a La to the alkaline earth metal molar ratio other than from about 0.01 : 1 to about 10.0: 1.
  • a method for producing olefins can comprise recovering at least a portion of the product mixture from the reactor.
  • a method for producing olefins can comprise recovering at least a portion of the C 2 hydrocarbons from the product mixture.
  • the product mixture can comprise C 2+ hydrocarbons (including olefins), unreacted methane, and optionally a diluent.
  • the water produced from the OCM reaction and the water used as a diluent can be separated from the product mixture prior to separating any of the other product mixture components. For example, by cooling down the product mixture to a temperature where the water condenses (e.g., below 100°C at ambient pressure), the water can be removed from the product mixture, by using a flash chamber for example.
  • At least a portion of the C 2+ hydrocarbons can be separated (e.g., recovered) from the product mixture to yield recovered C 2+ hydrocarbons.
  • the C 2+ hydrocarbons can be separated from the product mixture by using any suitable separation technique.
  • at least a portion of the C 2+ hydrocarbons can be separated from the product mixture by distillation (e.g., cryogenic distillation).
  • At least a portion of the recovered C 2+ hydrocarbons can be used for ethylene production.
  • at least a portion of ethylene can be separated from the product mixture (e.g., from the C 2+ hydrocarbons, from the recovered C 2+ hydrocarbons) to yield recovered ethylene and recovered hydrocarbons, by using any suitable separation technique (e.g., distillation).
  • at least a portion of the recovered hydrocarbons e.g., recovered C 2+ hydrocarbons after olefin separation, such as separation of C 2 H 4 and C 3 H 6
  • a method for producing olefins can comprise recovering at least a portion of the olefins from the product mixture.
  • at least a portion of the olefins can be separated from the product mixture by distillation (e.g., cryogenic distillation).
  • the olefins are generally individually separated from their paraffin counterparts by distillation (e.g., cryogenic distillation).
  • ethylene can be separated from ethane by distillation (e.g., cryogenic distillation).
  • propylene can be separated from propane by distillation (e.g., cryogenic distillation).
  • At least a portion of the unreacted methane can be separated from the product mixture to yield recovered methane.
  • Methane can be separated from the product mixture by using any suitable separation technique, such as for example distillation (e.g., cryogenic distillation).
  • At least a portion of the recovered methane can be recycled to the reactant mixture.
  • the OCM catalyst composition can be characterized by the general formula Sr a La b Yb c Ce d O x ; wherein a is 1.0; wherein b is from about 0.01 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5; wherein c is from about 0.01 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5; wherein d is from about 0.01 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5; and wherein x balances the oxidation states.
  • At least some of the Sr, La, Yb and Ce can have multiple oxidation states within the OCM catalyst composition, and as such x can have any suitable value that allows for the oxygen anions to balance all the cations.
  • the OCM catalyst composition can be characterized by the general formula Sr a La b Yb c Tm d O x ; wherein a is 1.0; wherein b is from about 0.01 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5; wherein c is from about 0.01 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5; wherein d is from about 0.01 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5; and wherein x balances the oxidation states.
  • At least some of the Sr, La, Yb and Tm can have multiple oxidation states within the OCM catalyst composition, and as such x can have any suitable value that allows for the oxygen anions to balance all the cations.
  • the OCM catalyst composition can be characterized by the general formula A a La b O x ; wherein A is an alkaline earth metal; wherein a is 1.0; wherein b is from about 0.01 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5; and wherein x balances the oxidation states.
  • a and/or La could have multiple oxidation states within the OCM catalyst composition, and as such x can have any suitable value that allows for the oxygen anions to balance all the cations.
  • the OCM catalyst composition characterized by the general formula A a La b O x
  • A is Sr.
  • the OCM catalyst composition can be characterized by the general formula Sr a La b O x ; wherein a is 1.0; wherein b is from about 0.01 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5; and wherein x balances the oxidation states.
  • the OCM catalyst composition can be characterized by the general formula A a La b E c O x ; wherein A is an alkaline earth metal; wherein E is a first rare earth element; wherein a is 1.0; wherein b is from about 0.01 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5; wherein c is from about 0.01 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5; and wherein x balances the oxidation states.
  • At least some of the A, La, and E can have multiple oxidation states within the OCM catalyst composition, and as such x can have any suitable value that allows for the oxygen anions to balance all the cations.
  • the OCM catalyst composition characterized by the general formula A a La b E c O x , A is Sr, and E is Yb.
  • the OCM catalyst composition can be characterized by the general formula Sr a La b Yb c O x ; wherein a is 1.0; wherein b is from about 0.01 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5; wherein c is from about 0.01 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5; and wherein x balances the oxidation states.
  • the OCM catalyst composition can be characterized by the general formula A a La b D d O x ; wherein A is an alkaline earth metal; wherein D is a redox agent; wherein a is 1.0; wherein b is from about 0.01 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5; wherein d is from about 0.01 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5; and wherein x balances the oxidation states.
  • At least some of the A, La, and D can have multiple oxidation states within the OCM catalyst composition, and as such x can have any suitable value that allows for the oxygen anions to balance all the cations.
  • the OCM catalyst composition characterized by the general formula A a La b D d O x , A is Sr, and D is Mn.
  • the OCM catalyst composition can be characterized by the general formula Sr a La b Mn d O x ; wherein a is 1.0; wherein b is from about 0.01 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5; wherein d is from about 0.01 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5; and wherein x balances the oxidation states.
  • the OCM catalyst composition characterized by the general formula A a La b D d O x
  • A is Sr
  • D is W
  • the OCM catalyst composition can be characterized by the general formula Sr a La b W d O x ; wherein a is 1.0; wherein b is from about 0.01 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5; wherein d is from about 0.01 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5; and wherein x balances the oxidation states.
  • a method of making an OCM catalyst composition can comprise the steps of (a) forming an OCM catalyst precursor aqueous solution comprising an alkaline earth metal nitrate, a La nitrate, a first rare earth element nitrate, and a redox agent nitrate or a second rare earth element nitrate; wherein the first rare earth element nitrate and the second rare earth element nitrate are different; wherein the OCM catalyst precursor aqueous solution is characterized by a molar ratio of La to alkaline earth metal of b: l, wherein b is from about 0.01 to about 10.0; wherein the OCM catalyst precursor aqueous solution is characterized by a molar ratio of first rare earth element to alkaline earth metal of c: l, wherein c is from about 0 to about 10.0; and wherein the OCM catalyst precursor aqueous solution is characterized by a molar ratio of redox agent or second rare earth element
  • a method for producing ethylene can comprise the steps of (a) introducing a reactant mixture to a reactor comprising an OCM catalyst composition; wherein the reactant mixture comprises CH 4 and 0 2 ; wherein the OCM catalyst composition is characterized by the general formula A a La b E c D d O x ; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein c is from about 0 to about 10.0; wherein d is from about 0 to about 10.0; and wherein x balances the oxidation states; (b) allowing at least a portion of the reactant mixture to contact at least a portion of the OCM catalyst composition and react via an OCM reaction to form a product mixture comprising olefins, wherein the olefins comprise ethylene; (c) recovering at least a portion of the product mixture from the reactor; and (d) recovering at least a portion of the ethylene from the product mixture.
  • the OCM catalyst compositions characterized by the general formula A a La b E c D d O x ; wherein A is an alkaline earth metal; wherein E is a first rare earth element; wherein D is a redox agent or a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein c is from about 0 to about 10.0; wherein d is from about 0 to about 10.0; and wherein x balances the oxidation states; and methods of making and using same, as disclosed herein can advantageously display improvements in one or more composition characteristics when compared to an otherwise similar OCM catalyst composition (i) without La, or (ii) comprising an alkaline earth metal and La in a La to the alkaline earth metal molar ratio other than from about 0.01 : 1 to about 10.0: 1.
  • the OCM catalyst compositions characterized by the general formula A a La b E c D d O x ; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein c is from about 0 to about 10.0; wherein d is from about 0 to about 10.0; and wherein x balances the oxidation states; can display improved conversion and selectivity, when compared to the conversion and selectivity, respectively, of an otherwise similar OCM catalyst composition (i) without La, or (ii) comprising an alkaline earth metal and La in a La to the alkaline earth metal molar ratio other than from about 0.01 : 1 to about 10.0: 1.
  • a highly selective catalyst such as the OCM catalysts disclosed herein, can advantageously reduce the heat produced in the process, such that the reactor can be easier to control and operate.
  • a highly active catalyst in terms of conversion
  • some conventional OCM catalysts such as the Mn-Na 2 W0 4 /Si0 2 catalyst, require for the feed to the reactor to be pre-heated to about 800°C, which translates in a high energy cost, as well as expensive specialized materials for a heat exchanger used for pre-heating the reactor feed.
  • the composition of OCM catalyst compositions characterized by the general formula A a La b E c D d O x ; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein c is from about 0 to about 10.0; wherein d is from about 0 to about 10.0; and wherein x balances the oxidation states; as disclosed herein can be advantageously adjusted as necessary, based on the needs of the OCM reaction, to meet target criteria, such as a target selectivity and/or a target conversion, owing to a broader range of A, La, E and D content; and as such the OCM catalyst compositions as disclosed herein can display better performance when compared to otherwise similar OCM catalyst compositions (i) without La, or (ii) comprising an alkaline earth metal and La in a La to the alkaline earth metal molar ratio other than from about 0.01 : 1 to about 10.0: 1.
  • the OCM catalyst compositions characterized by the general formula A a La b E c D d O x ; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein c is from about 0 to about 10.0; wherein d is from about 0 to about 10.0; and wherein x balances the oxidation states; can advantageously display an enhanced stability of performance (e.g., in terms of conversion and selectivity) over time when compared to the stability of performance of an otherwise similar OCM catalyst composition (i) without La, or (ii) comprising an alkaline earth metal and La in a La to the alkaline earth metal molar ratio other than from about 0.01 : 1 to about 10.0: 1.
  • an enhanced stability of performance e.g., in terms of conversion and selectivity
  • the OCM catalyst compositions characterized by the general formula A a La b E c D d O x as disclosed herein can maintain improved conversion and selectivity over a time frame that is greater than a time frame where an otherwise similar OCM catalyst composition (i) without La, or (ii) comprising an alkaline earth metal and La in a La to the alkaline earth metal molar ratio other than from about 0.01 : 1 to about 10.0: 1, can maintain its conversion and selectivity values.
  • the performance of catalysts can degrade (e.g., decay), owing to catalyst deactivation; and the longer a catalyst can maintain a desired performance (e.g., in terms of conversion and selectivity), the better the catalyst is.
  • OCM catalyst compositions characterized by the general formula A a La b E c D d O x ; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein c is from about 0 to about 10.0; wherein d is from about 0 to about 10.0; and wherein x balances the oxidation states; and methods of making and using same, as disclosed herein can be apparent to one of skill in the art viewing this disclosure.
  • Oxidative coupling of methane (OCM) catalyst compositions were prepared as follows.
  • a reference catalyst composition following the general formula Sr ! oCeo gYbo iO was prepared as follows. In an attempt to produce 10 g of Sr 1 0 Ce 0 9 Yb 0 iO, 4.23 g of Sr(N0 3 ) 2 , 7.82 g of Ce(N0 3 ) 3 x 6H 2 0 and 0.90 g of Yb(N0 3 ) 3 x 5H 2 0 were added into 25 ml deionized (DI) water to provide a mixture, which mixture was further agitated until all solids were dissolved and a clear solution was obtained.
  • DI deionized
  • the obtained clear solution was dried at 125°C overnight to produce a dried OCM catalyst precursor mixture.
  • the dried OCM catalyst precursor mixture was calcined under air flow at 900°C for 6 hours to produce the reference catalyst #1 (e.g., Sr 1. oCeo .9 Ybo .1 O catalyst).
  • the obtained clear solution was dried at 125°C overnight to produce a dried OCM catalyst precursor mixture.
  • the dried OCM catalyst precursor mixture was calcined under air flow at 900°C for 6 hours to produce catalyst #3 (e.g., Sri oLao gYbo 1 O catalyst).
  • Other catalysts e.g., catalysts #1, #2, #4, #5, #6, and #7 with different amounts of La as compared to catalyst #3 were prepared in a similar fashion, but with using different amounts of La(N0 ) x 6H 2 0, as necessary.
  • Catalysts containing both La and Ce (e.g., catalysts #8, and #9), and well as catalysts containing both La and Tm (e.g., catalysts #10, and #1 1) were prepared in a manner similar to preparing the reference catalyst #1 and catalyst #3, by using the corresponding amounts of La(N0 ) x 6H 2 0, Ce(N0 ) x 6H 2 0, and Tm nitrate, as necessary to obtain a catalyst with the desired general formula.
  • OCM reactions were conducted by using catalysts prepared as described in Example 1 as follows.
  • a mixture of methane and oxygen along with an internal standard, an inert gas (neon) were fed to a quartz reactor with an internal diameter (I.D.) of 2.3 mm heated by traditional clamshell furnace.
  • a catalyst (e.g., catalyst bed) loading was 20 mg or 10 mg, and a total flow rate of reactants was 40 standard cubic centimeters per minute (seem).
  • the reactor was first heated to a desired temperature under an inert gas flow and then a desired gas mixture was fed to the reactor.
  • All OCM reactions were conducted at a methane to oxygen (CH 4 :0 2 ) molar ratio of 7.4 and at a reactor temperature of 750°C.
  • the products obtained from the OCM reaction were analyzed by using an online Agilent 7890 gas chromatograph (GC) with a thermal conductivity detector (TCD) and a flame ionization detector (FID).
  • GC gas
  • catalyst #3 prepared as described in Example 1 was further investigated. OCM reactions were conducted as described in Example 2, at a reactor temperature of 800°C, and the stability of the catalyst was recorded over a period of more than 60 hours, in terms of 0 2 conversion (displayed in Figure #1); and CH 4 conversion and C 2+ selectivity (displayed in Figure 2). As displayed in Figures 1 and 2, catalyst #3 displayed stable performance over the tested time period, in terms of conversion and selectivity.
  • catalyst #3 was further compared with the performance of an extensively studied catalyst, Mn-Na 2 W0 4 /Si0 2 (reference catalyst #2), in order to demonstrate advantages of the OCM catalyst compositions disclosed herein.
  • Reference catalyst #2 was prepared by using the following method described below.
  • a stability test of the reference catalyst #2 was conducted as follows. A mixture of methane and oxygen along with an internal standard, an inert gas (argon) were fed to a quartz reactor with an internal diameter (I.D.) of 5.0 mm heated by traditional clamshell furnace. A catalyst (e.g., catalyst bed) loading was 250 mg, and a total flow rate of reactants was 100 standard cubic centimeters per minute (seem). The reactor was first heated to a desired temperature under an inert gas flow and then a desired gas mixture was fed to the reactor. All OCM reactions were conducted at a methane to oxygen (CH 4 :0 2 ) molar ratio of 7.4 and at a reactor temperature of 825°C.
  • CH 4 :0 2 methane to oxygen
  • a first aspect which is an oxidative coupling of methane (OCM) catalyst composition characterized by the general formula A a La b E c D d O x ; wherein A is an alkaline earth metal; wherein E is a first rare earth element; wherein D is a redox agent or a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein c is from about 0 to about 10.0; wherein d is from about 0 to about 10.0; and wherein x balances the oxidation states.
  • OCM oxidative coupling of methane
  • a second aspect which is the OCM catalyst composition of the first aspect, wherein the alkaline earth metal is selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and combinations thereof.
  • a third aspect which is the OCM catalyst composition of any one of the first and the second aspects, wherein the first rare earth element and the second rare earth element can each independently be selected from the group consisting of scandium (Sc), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), yttrium (Y), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), and combinations thereof.
  • Sc scandium
  • Ce cerium
  • Pr praseodymium
  • Nd neodymium
  • Pm promethium
  • Sm samarium
  • Eu europium
  • Gd gadolinium
  • Y yttrium
  • Tb terb
  • a fourth aspect which is the OCM catalyst composition of any one of the first through the third aspects, wherein the redox agent is selected from the group consisting of manganese (Mn), tungsten (W), bismuth (Bi), antimony (Sb), tin (Sn), cerium (Ce), praseodymium (Pr), and combinations thereof.
  • a fifth aspect which is the OCM catalyst composition of any one of the first through the fourth aspects comprising one or more oxides of A; one or more oxides of La; one or more oxides of E; one or more oxides of D; or combinations thereof.
  • a sixth aspect which is the OCM catalyst composition of any one of the first through the fifth aspects having the general formula Sr a La b Yb c Ce d O x ; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein c is from about 0.01 to about 10.0; wherein d is from about 0.01 to about 10.0; and wherein x balances the oxidation states.
  • a seventh aspect which is the OCM catalyst composition of any one of the first through the fifth aspects having the general formula Sr a La b Yb c Tm d O x ; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein c is from about 0.01 to about 10.0; wherein d is from about 0.01 to about 10.0; and wherein x balances the oxidation states.
  • An eighth aspect which is the OCM catalyst composition of any one of the first through the fifth aspects having the general formula A a La b O x ; wherein A is an alkaline earth metal; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; and wherein x balances the oxidation states.
  • a ninth aspect which is the OCM catalyst composition of the eighth aspect having the general formula Sr a La b O x ; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; and wherein x balances the oxidation states.
  • a tenth aspect which is the OCM catalyst composition of any one of the first through the fifth aspects having the general formula A a La b E c O x ; wherein A is an alkaline earth metal; wherein E is a first rare earth element; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein c is from about 0.01 to about 10.0; and wherein x balances the oxidation states.
  • An eleventh aspect which is the OCM catalyst composition of the tenth aspect having the general formula Sr a La b Yb c O x ; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein c is from about 0.01 to about 10.0; and wherein x balances the oxidation states.
  • a twelfth aspect which is the OCM catalyst composition of any one of the first through the fifth aspects having the general formula A a La b D d O x ; wherein A is an alkaline earth metal; wherein D is a redox agent; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein d is from about 0.01 to about 10.0; and wherein x balances the oxidation states.
  • a thirteenth aspect which is the OCM catalyst composition of the twelfth aspect having the general formula Sr a La b Mn d O x ; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein d is from about 0.01 to about 10.0; and wherein x balances the oxidation states.
  • a fourteenth aspect which is the OCM catalyst composition of the twelfth aspect having the general formula Sr a La b W d O x ; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein d is from about 0.01 to about 10.0; and wherein x balances the oxidation states.
  • a fifteenth aspect which is the OCM catalyst composition of any one of the first through the fourteenth aspects further comprising a support, wherein at least a portion of the OCM catalyst composition contacts, coats, is embedded in, is supported by, and/or is distributed throughout at least a portion of the support; wherein the support comprises MgO, A1 2 0 3 , Si0 2 , Zr0 2 , Ti0 2 , or combinations thereof; and wherein the support is in the form of powders, particles, pellets, monoliths, foams, honeycombs, or combinations thereof.
  • a sixteenth aspect which is the OCM catalyst composition of any one of the first through the fifteenth aspects, wherein the OCM catalyst composition is characterized by a C 2+ selectivity that is increased by equal to or greater than about 2%, when compared to a C 2+ selectivity of an otherwise similar OCM catalyst composition (i) without La, or (ii) comprising an alkaline earth metal and La in a La to the alkaline earth metal molar ratio other than from about 0.01 : 1 to about 10.0: 1.
  • a seventeenth aspect which is the OCM catalyst composition of any one of the first through the sixteenth aspects, wherein the OCM catalyst composition is characterized by a CH 4 conversion that is increased by equal to or greater than about 1%, when compared to a CH 4 conversion of an otherwise similar OCM catalyst composition (i) without La, or (ii) comprising an alkaline earth metal and La in a La to the alkaline earth metal molar ratio other than from about 0.01 : 1 to about 10.0: 1.
  • An eighteenth aspect which is the OCM catalyst composition of any one of the first through the seventeenth aspects, wherein the OCM catalyst composition is characterized by a reactor temperature effective for achieving an 0 2 conversion of equal to or greater than about 90% that is decreased by equal to or greater than about 25°C, when compared to a reactor temperature effective for achieving an 0 2 conversion of equal to or greater than about 90% of an otherwise similar OCM catalyst composition (i) without La, or (ii) comprising an alkaline earth metal and La in a La to the alkaline earth metal molar ratio other than from about 0.01 : 1 to about 10.0: 1.
  • a nineteenth aspect which is a method of making an oxidative coupling of methane (OCM) catalyst composition
  • OCM methane
  • the OCM catalyst precursor mixture comprises one or more compounds comprising an alkaline earth metal cation, one or more compounds comprising a La cation, one or more compounds comprising a first rare earth element cation, and one or more compounds comprising a redox agent cation or a second rare earth element cation; wherein the first rare earth element cation and the second rare earth element cation are different;
  • the OCM catalyst precursor mixture is characterized by a molar ratio of La to alkaline earth metal of b: l, wherein b is from about 0.01 to about 10.0;
  • the OCM catalyst precursor mixture is characterized by a molar ratio of first rare earth element to alkaline earth metal of c: l, wherein c is from about 0 to about 10.0; and wherein the OCM catalyst precursor mixture is
  • a twentieth aspect which is the method of the nineteenth aspect, wherein the step (a) of forming an OCM catalyst precursor mixture further comprises (i) solubilizing the one or more compounds comprising an alkaline earth metal cation, one or more compounds comprising a La cation, one or more compounds comprising a first rare earth element cation, and one or more compounds comprising a redox agent cation or a second rare earth element cation in an aqueous medium to form an OCM catalyst precursor aqueous solution; and (ii) drying at least a portion of the OCM catalyst precursor aqueous solution to form the OCM catalyst precursor mixture.
  • a twenty-first aspect which is the method of the twentieth aspect, wherein the OCM catalyst precursor aqueous solution is dried at a temperature of equal to or greater than about 75°C.
  • a twenty-second aspect which is the method of any one of the nineteenth through the twenty-first aspects, wherein at least a portion of the OCM catalyst precursor aqueous solution is contacted with a support to yield a supported OCM catalyst precursor.
  • a twenty-third aspect which is the method of the twenty-second aspect, wherein at least a portion of the supported OCM catalyst precursor is further dried and calcined to form the OCM catalyst composition.
  • a twenty-fourth aspect which is the method of any one of the nineteenth through the twenty- third aspects, wherein the OCM catalyst precursor mixture is calcined at a temperature of equal to or greater than about 750°C.
  • a twenty-fifth aspect which is the method of any one of the nineteenth through the twenty- fourth aspects, wherein the one or more compounds comprising an alkaline earth metal cation comprises an alkaline earth metal nitrate, an alkaline earth metal oxide, an alkaline earth metal hydroxide, an alkaline earth metal chloride, an alkaline earth metal acetate, an alkaline earth metal carbonate, or combinations thereof; wherein the one or more compounds comprising a La cation comprises a La nitrate, a La oxide, a La hydroxide, a La chloride, a La acetate, a La carbonate, or combinations thereof; wherein the one or more compounds comprising a first rare earth element cation comprises a first rare earth element nitrate, a first rare earth element oxide, a first rare earth element hydroxide, a first rare earth element chloride, a first rare earth element acetate, a first rare earth element carbonate, or combinations thereof; wherein the one or more compounds comprising an al
  • a twenty-sixth aspect which is an OCM catalyst produced by the method of any one of the nineteenth through the twenty-fifth aspects.
  • a twenty-seventh aspect which is a method of making an oxidative coupling of methane (OCM) catalyst composition
  • OCM methane
  • a method of making an oxidative coupling of methane (OCM) catalyst composition comprising (a) forming an OCM catalyst precursor aqueous solution comprising an alkaline earth metal nitrate, a La nitrate, a first rare earth element nitrate, and a redox agent nitrate or a second rare earth element nitrate; wherein the first rare earth element nitrate and the second rare earth element nitrate are different; wherein the OCM catalyst precursor aqueous solution is characterized by a molar ratio of La to alkaline earth metal of b: l, wherein b is from about 0.01 to about 10.0; wherein the OCM catalyst precursor aqueous solution is characterized by a molar ratio of first rare earth element to alkaline earth metal of c: l, wherein c is from about
  • a twenty-eighth aspect which is an oxidative coupling of methane (OCM) catalyst composition produced by (a) solubilizing one or more compounds comprising an alkaline earth metal cation, one or more compounds comprising a La cation, one or more compounds comprising a first rare earth element cation, and one or more compounds comprising a redox agent cation or second rare earth element cation in an aqueous medium to form an OCM catalyst precursor aqueous solution; wherein the first rare earth element cation and the second rare earth element cation are different; wherein the OCM catalyst precursor aqueous solution is characterized by a molar ratio of La to alkaline earth metal of b: l, wherein b is from about 0.01 to about 10.0; wherein the OCM catalyst precursor aqueous solution is characterized by a molar ratio of first rare earth element to alkaline earth metal of c: l, wherein c is from about 0 to about 10.0;
  • a twenty-ninth aspect which is a method for producing olefins comprising (a) introducing a reactant mixture to a reactor comprising an oxidative coupling of methane (OCM) catalyst composition; wherein the reactant mixture comprises methane (CH 4 ) and oxygen (0 2 ); wherein the OCM catalyst composition is characterized by the general formula A a La b E c D d O x ; wherein A is an alkaline earth metal; wherein E is a first rare earth element; wherein D is a redox agent or a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; wherein c is from about 0 to about 10.0; wherein d is from about 0 to about 10.0; and wherein x balances the oxidation states; (b) allowing at least a portion of the reactant mixture to contact at least a portion of the
  • a thirtieth aspect which is the method of the twenty-ninth aspect, wherein the reactor is characterized by a reactor temperature effective for achieving an 0 2 conversion of equal to or greater than about 90% that is decreased by equal to or greater than about 25°C, when compared to a reactor temperature effective for achieving an 0 2 conversion of equal to or greater than about 90% of a reactor comprising an otherwise similar OCM catalyst composition (i) without La, or (ii) comprising an alkaline earth metal and La in a La to the alkaline earth metal molar ratio other than from about 0.01 : 1 to about 10.0: 1.

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Abstract

L'invention concerne une composition de catalyseur OCM caractérisée par la formule générale AaLabEcDdOx ; dans laquelle A est un métal alcalino-terreux ; E est un premier élément des terres rares ; D est un agent d'oxydoréduction ou un second élément des terres rares ; le premier élément des terres rares et le second élément des terres rares étant différents ; a est égal à 1,0 ; b est compris entre 0,01 et 10,0 ; c est compris entre 0 et 10,0 ; d est compris entre 0 et 10,0 ; et x équilibre les états d'oxydation. Le métal alcalino-terreux est choisi dans le groupe constitué par le Mg, le Ca, le Sr, le Ba, et leurs combinaisons. Le premier élément des terres rares et le second élément des terres rares peuvent chacun indépendamment être choisis dans le groupe constitué par le Sc, le Ce, le Pr, le Nd, le Pm, le Sm, l'Eu, le Gd, l'Y, le Tb, le Dy, l'Ho, l'Er, le Tm, l'Yb, le Lu, et leurs combinaisons. L'agent d'oxydoréduction est choisi dans le groupe constitué par le Mn, le W, le Bi, le Sb, le Sn, le Ce, le Pr, et leurs combinaisons.
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